CN114505474B - Multi-morphology low-temperature sinterable nano silver and preparation method and application thereof - Google Patents
Multi-morphology low-temperature sinterable nano silver and preparation method and application thereof Download PDFInfo
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- CN114505474B CN114505474B CN202210092927.7A CN202210092927A CN114505474B CN 114505474 B CN114505474 B CN 114505474B CN 202210092927 A CN202210092927 A CN 202210092927A CN 114505474 B CN114505474 B CN 114505474B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 239000000919 ceramic Substances 0.000 claims abstract description 9
- 239000002086 nanomaterial Substances 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 5
- 238000005119 centrifugation Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 239000002105 nanoparticle Substances 0.000 claims description 15
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 239000012265 solid product Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical group [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002135 nanosheet Substances 0.000 claims description 6
- 239000002073 nanorod Substances 0.000 claims description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 238000005189 flocculation Methods 0.000 claims description 2
- 230000016615 flocculation Effects 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 229960004063 propylene glycol Drugs 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 abstract description 27
- 239000004332 silver Substances 0.000 abstract description 27
- 239000007788 liquid Substances 0.000 abstract description 21
- 239000006185 dispersion Substances 0.000 abstract description 14
- 238000009766 low-temperature sintering Methods 0.000 abstract description 9
- 239000000843 powder Substances 0.000 abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 abstract description 7
- 238000006722 reduction reaction Methods 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000005416 organic matter Substances 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 238000005374 membrane filtration Methods 0.000 abstract 1
- 238000004062 sedimentation Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000000203 mixture Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- 238000005245 sintering Methods 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000001000 micrograph Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000003223 protective agent Substances 0.000 description 4
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 4
- 229940071536 silver acetate Drugs 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- -1 silver ions Chemical class 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-N L-arginine Chemical compound OC(=O)[C@@H](N)CCCN=C(N)N ODKSFYDXXFIFQN-BYPYZUCNSA-N 0.000 description 1
- 229930064664 L-arginine Natural products 0.000 description 1
- 235000014852 L-arginine Nutrition 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- JKOCEVIXVMBKJA-UHFFFAOYSA-M silver;butanoate Chemical compound [Ag+].CCCC([O-])=O JKOCEVIXVMBKJA-UHFFFAOYSA-M 0.000 description 1
- DOQQTKLDEQSKIE-UHFFFAOYSA-N silver;isocyanate Chemical compound [Ag+].[N-]=C=O DOQQTKLDEQSKIE-UHFFFAOYSA-N 0.000 description 1
- ZYPJJPHRTZPKKY-UHFFFAOYSA-M silver;octanoate Chemical compound [Ag+].CCCCCCCC([O-])=O ZYPJJPHRTZPKKY-UHFFFAOYSA-M 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
A multi-morphology low-temperature sinterable nano silver and a preparation method and application thereof belong to the technical field of metal nano materials. The method of the invention comprises the following steps: dispersing a precursor of insoluble silver salt in a solution of a polymer dispersing agent to form a dispersion liquid, carrying out chemical reduction by heating and stirring to obtain a dispersion liquid containing nano silver, separating and purifying by steps of poor solvent sedimentation, redispersion, centrifugation, ceramic membrane filtration and the like, and finally obtaining the multi-morphology nano silver powder by freeze drying. The nano silver prepared by the invention comprises granular, flaky, rod-like and other shapes. The preparation method is simple and controllable, has low cost, has the organic matter content on the surface of the nano silver after being cleaned for multiple times lower than 0.5%, shows good low-temperature sintering characteristic, and has the volume resistivity which is only about 3 times that of the bulk silver after being sintered.
Description
Technical Field
The invention belongs to the technical field of metal nano materials, and particularly relates to a polymorphic low-temperature sinterable nano silver, a preparation method and application thereof.
Background
Nano silver can be sintered at a melting point far lower than that of bulk silver due to its higher surface energy. The nano silver capable of being sintered at low temperature plays an important role in the fields of electronic circuits and communication, and is mainly prepared into various conductive pastes or inks to be further used for preparing electrodes, welding bodies and surface coatings of printed circuits or electronic elements so as to play roles of electric conduction, heat conduction, mechanical adhesion or electromagnetic shielding.
The low-temperature sintering of the nano silver can realize lattice-level connection among particles, greatly reduce contact resistance among the particles, and remarkably improve the electric conduction, heat conduction and mechanical properties of the whole prepared structure. The nano silver capable of being sintered at low temperature needs to have higher surface activity, and generally the smaller the size of the nano silver, the fewer impurities adsorbed on the surface, the easier the sintering. The overall properties of the sintered body are also related to the morphology of the nanosilver, the bulk density of the particles, and the structure of the sintered body. Because of the low bulk density, the zero-dimensional nanoparticles form a large number of voids and interstices after sintering, which makes it difficult to form a high quality sintered body. The two-dimensional nano-sheets and the one-dimensional nano-rods can provide a wider range of conductive paths, and improve the performance of the sintered body. However, the surface of the silver nano material with one-dimensional and two-dimensional morphology is mainly exposed with a low energy surface, and the sintering activity is lower than that of nano particles. The nano silver materials with different morphologies are mixed together for sintering, so that the advantages of the nano silver with different morphologies can be fully exerted, the performance of the sintered body is enhanced, and the method is specifically shown as follows: one-and two-dimensional nanoparticles can provide long Cheng Daodian pathways; the high sintering activity of the zero-dimensional nano particles can promote the sintering of the whole body; the mixing of the polymorphic nano silver can improve the overall bulk density and further improve the overall sintering performance of the sintered body. Thus, the multi-morphology mixed silver nanomaterial is an effective way to construct high performance nano silver sintered bodies.
The current preparation methods of nano silver can be mainly divided into a physical method and a chemical method. The physical method comprises a mechanical ball milling method, an evaporation condensation method and a laser ablation method, and the methods have the defects of high equipment cost, high energy consumption, low production efficiency and the like. The chemical method comprises a liquid phase chemical reduction method, a microemulsion method, a solvothermal method, a template method seed crystal method, a photoinduction method and an electrochemical reduction method chemical method, wherein the liquid phase chemical reduction method is the most widely applied method for preparing nano silver in batches at present due to the advantages of mild conditions, high yield, low cost, high repeatability and the like. The Chinese patent with application publication number of CN 109264766A utilizes an interface reaction template between polysaccharide polyelectrolytes to perform hydrothermal reduction reaction or double decomposition reaction of metal salt, so as to obtain the nano particles with different morphologies. The Chinese patent with the publication number of CN 105921765B is issued to disperse spherical nano silver powder in a lipid solvent for treatment, and then the rod-shaped silver powder with the length of 600-2000nm is obtained through the steps of cleaning, drying and the like. The Chinese patent with application publication number of CN 111659900A dissolves silver salt in organic amine for heat treatment to obtain granular nano silver with particle size of 10-150nm and low temperature sintering performance. The Chinese patent with application publication number of CN 108015299A adds silver salt, reducer and surfactant into solvent to react to obtain nano silver particles with uniform particle size distribution, but the conductivity of silver paste composed of nano particles obtained by the method needs to be improved, because the residual amount of organic matters on the surfaces of the nano particles is high, and the nano particles are difficult to sinter at low temperature. Liu Dongzhi et al synthesized silver nanoparticles with the narrowest particle size distribution of 10.+ -.2 nm and 11.+ -.2 nm by a one-pot method using L-arginine as a protective agent and a reducing agent and silver nitrate or silver acetate as a precursor, and further obtained a conductive film with a resistivity of only 3.8. Mu. OMEGA.cm. The Chinese patent with application publication number CN 108372310A discloses a preparation method of small-size nano silver for water-based conductive ink. However, the preparation method of the polymorphic nano silver has poor controllability. Due to the excessive number of explosive nucleation of silver ions in a homogeneous system, there is a tendency to produce nano silver materials of uniform size and shape. The nano silver prepared by the traditional chemical method has single size and shape, higher content of surface coating, poor sintering performance, small yield and difficult industrialization. Mainly prepared by nano silver with single morphology and size, is difficult to realize the one-time preparation of multi-morphology nano silver, and has low-temperature sintering performance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a multi-morphology low-temperature sinterable nano silver, and a preparation method and application thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the polymorphic low-temperature sinterable nano silver is characterized by comprising the following steps of:
(1) Weighing insoluble silver salt, adding the insoluble silver salt into a solvent containing 5% -20% of polymer dispersing agent, and alternately carrying out mechanical stirring and ultrasonic dispersing for 10-60min to obtain uniform mixed solution A;
(2) Heating the mixed solution A obtained in the step (1) to 80-140 ℃ under stirring, preserving heat for 1-12h, and naturally cooling to room temperature to obtain a mixed solution B containing nano silver products;
(3) Adding a poor solvent of the polymer dispersing agent into the mixed solution B obtained in the step (2) under stirring, stirring until flocculation occurs, stopping stirring, naturally settling flocculate at the bottom of the reactor, and standing to obtain precipitate;
(4) Dispersing the precipitate in an alcohol solvent by stirring and ultrasonic, centrifuging, collecting a solid product, dispersing in the alcohol solvent, filtering for 3-5 times to remove excessive polymer dispersing agent on the surface of nano silver, centrifuging to obtain a solid product, dissolving in water, and freeze-drying to obtain the multi-morphology low-temperature sinterable nano silver.
The preparation method of the polymorphic low-temperature sinterable nano silver is characterized in that the mass-volume ratio of the poorly soluble silver salt to the solvent in the step (1) is 0.3-2kg/L, the speed of mechanical stirring is 100-500r/min, and the power of ultrasonic dispersion is 50-300W.
The preparation method of the polymorphic low-temperature sinterable nano silver is characterized in that the insoluble silver salt in the step (1) comprises at least one of silver acetate, silver butyrate, silver caproate, silver caprylate, silver oxalate, silver isocyanate, silver chloride, silver bromide, silver iodide, silver carbonate and silver sulfate, preferably silver oxalate;
the polymer dispersant comprises at least one of polyvinylpyrrolidone with an average molecular weight of 10000-360000;
the solvent comprises at least one of water, ethylene glycol, diethylene glycol, polyethylene glycol, glycerol, 1, 2-propylene glycol, benzyl alcohol and n-butanol.
The preparation method of the polymorphic low-temperature sinterable nano silver is characterized in that the volume ratio of the poor solvent of the polymer dispersing agent in the step (3) to the solvent in the step (1) is 1-3:1.
The preparation method of the polymorphic low-temperature sinterable nano silver is characterized in that the centrifugation condition in the step (4) is as follows: the centrifugal speed is 3000-8000r/min, the centrifugal time is 10-30min, and the filtering comprises adopting ceramic membrane dynamic circulation filtering equipment.
The preparation method of the polymorphic low-temperature sinterable nano silver is characterized in that the aperture of the ceramic membrane dynamic circulation filtering equipment is 20-100nm, and the pressure difference is 0.01-0.3MPa.
The preparation method of the polymorphic low-temperature sinterable nano silver is characterized in that the alcohol solvent in the step (4) comprises at least one of ethanol, isopropanol, ethylene glycol, n-propanol, n-butanol, diethylene glycol and benzyl alcohol.
A polymorphic low temperature sinterable nanosilver characterized by being obtainable by employing said preparation method.
The multi-morphology low-temperature sinterable nano-silver is characterized in that the multi-morphology low-temperature sinterable nano-silver comprises at least one of nano-particles, nano-sheets and nano-rods;
the particle size of the nano particles is 20-150nm, the sheet diameter of the nano sheet is 200-5000nm, the thickness is 20-100nm, the diameter of the nano rod is 30-100nm, and the length is 1-10 mu m.
The multi-morphology low-temperature sintered nano silver can be applied to metal nano materials.
The invention uses indissolvable silver salt as a reaction raw material, and performs the reaction in a heterogeneous system, so that the nucleation quantity of nano silver in the initial stage of the reaction can be reduced, and the slow growth of nano silver crystals is facilitated. And the function of the protective agent can limit the infinite growth of the nano particles, thereby obtaining the nano silver with specific size and shape. On the other hand, when the content of the protecting agent on the nano silver surface is too high and it is difficult to remove from the nano particle surface, it becomes an obstacle to nano silver sintering. Therefore, the composition and content of the protective agent on the nano silver surface are strictly controlled. The shape and the particle size distribution of the nano silver can be regulated and controlled by regulating the components and the proportion of the silver source, the dispersing agent, the reducing agent and the solvent.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method is characterized in that insoluble silver salt is used as a precursor, mild and environment-friendly reducing solvent and polymer surface dispersing agent are utilized to control the nucleation quantity and growth rate of nano silver, and the nano silver with multiple morphologies and wide particle size distribution is synthesized by a one-step method.
(2) In a heterogeneous system containing insoluble silver salt and a polymer dispersing agent, the multi-morphology low-temperature sinterable nano silver is prepared in a large scale by a chemical reduction method. The multi-morphology nano silver is prepared in a large scale by a one-pot method, the preparation process is simple, the morphology and the size distribution of the nano silver are adjustable, the content of the surface coating is low, and the low-temperature sintering performance is good. The method of the invention improves the efficiency, reduces the cost and has low organic matter content on the nano silver surface. The method has the advantages of simple process, controllable reaction, environmental protection, low cost and capability of realizing mass production.
(3) The multi-morphology nano silver prepared by the method has the residual organic matter content of less than 0.5 percent, has good low-temperature sintering performance, can realize sintering after being treated for 30 minutes at 175 ℃, and has the resistivity of only 5 multiplied by 10 -6 The volume resistivity of the nano silver after sintering is only about 3 times of that of the bulk silver.
Drawings
FIG. 1 is a scanning electron microscope image of the nano silver mixed in the shape of particles and oval sheets prepared in example 1;
FIG. 2 is a scanning electron microscope image of the nano-silver prepared in example 1 after 30min treatment at 175 ℃;
FIG. 3 is a scanning electron microscope image of the granular, plate-like and rod-like mixed nano silver prepared in example 2;
FIG. 4 is a scanning electron microscope image of the nano-silver prepared in example 2 after 30min treatment at 175 ℃;
FIG. 5 is a scanning electron microscope image of granular, triangular and hexagonal plate-shaped nano-silver prepared in example 3;
FIG. 6 is a scanning electron microscope image of the nano-silver prepared in example 3 after 30min treatment at 175 ℃;
FIG. 7 is a scanning electron microscope image of the granular nano-silver of comparative example 1;
FIG. 8 is a scanning electron microscope image of the silver powder of the comparative example 2 μm-sized;
fig. 9 is a scanning electron microscope image of the unreduced silver salt of comparative example 3.
Detailed Description
The preparation of the process according to the invention is illustrated in more detail by the following examples. It should be noted that the following examples are only for illustrating the preparation process of the present invention, and are not intended to limit the scope of the present invention.
Example 1: preparation of granular and flaky nano silver mixed nano silver
The preparation method of the granular and flaky nano silver mixture comprises the following steps: at normal temperature, 10g PVP with an average molecular weight of 29000 is dissolved in 100mL ethylene glycol by continuous stirring; then dispersing 10g of silver oxalate in the PVP solution, and carrying out alternating treatment of stirring and ultrasonic treatment to obtain uniform dispersion liquid without precipitation; transferring the dispersion liquid into an oil bath heated reaction kettle, heating the mixed liquid to 100 ℃ under the condition of continuous stirring, reacting at constant temperature for 12 hours, stopping heating, and naturally cooling the reaction system to room temperature. Adding 300mL of acetone into the mixture after reaction under continuous stirring, standing for 30min, naturally settling nano silver, pouring out supernatant, dispersing precipitate containing nano silver into 500mL of ethanol, centrifuging for 30min under the condition of 3000rpm, and cleaning to obtain precipitate; and then repeatedly washing for 5 times through ceramic membrane dynamic filtration, finally centrifuging to obtain a solid product, dispersing the solid product in 100mL of water, and obtaining silver powder for later use through freeze drying. The prepared nano silver mainly comprises two shapes of particles and flakes, wherein the particle size of the particle nano silver is 50-150nm, the flake nano silver is mainly elliptical, the flake diameter is about 200-800nm, and the thick bottom is about 50-100nm. Dispersing the above nanometer silver in isopropanol to obtain silver slurry with solid content of 50%, blade coating to obtain coating with thickness of 20 μm, treating at 175 deg.C for 30min, and measuring resistivity of 6×10 -6 Omega cm. Fig. 1 is a scanning electron micrograph of the particulate and platelet-shaped nano-silver mixture prepared as described above. As can be seen from FIG. 1, the nano silver mainly comprises two types of nano particles and nano sheets, the particle size distribution is wide, and the nano silver with different shapes and particle sizes is mixedIs more uniform. FIG. 2 is a low temperature sintered morphology thereof.
Example 2: preparation of granular, flaky and linear mixed nano silver
The preparation method of the granular, flaky and linear nano silver mixture comprises the following steps: at normal temperature, 10g PVP with average molecular weight of 58000 is dissolved in 100mL deionized water by continuous stirring; then dispersing 10g of silver oxalate powder in the PVP solution, and stirring and carrying out ultrasonic treatment to obtain a uniform dispersion liquid without precipitation; transferring the dispersion liquid into an oil bath heated reaction kettle, heating the mixed liquid until boiling and reacting for 2 hours at constant temperature under the condition of continuously stirring, stopping heating, and naturally cooling the reaction system to room temperature. Adding 250mL of acetone into the mixture after reaction under continuous stirring, standing for 30min, naturally settling nano silver, pouring out supernatant, dispersing precipitate containing nano silver into 500mL of ethanol, and centrifuging for 30min under the condition of 3000rpm to clean nano silver to obtain precipitate; repeatedly cleaning for 5 times through ceramic membrane dynamic filtration, finally centrifuging to obtain a solid product, and adding 1:1, mixing the isopropyl alcohol into paste silver paste by using a planetary mixing device for standby. The prepared nano silver comprises particles, flakes and rods, wherein the particle size of the particles is 50-150nm, the flakes of the nano silver comprise triangular shapes and hexagonal shapes, the flake diameter is about 200-800nm, the thick bottom is about 50nm, the diameter of the rods of the nano silver is about 50-100nm, and the length is about 1-3 mu m. Dispersing the above nanometer silver in isopropanol to obtain silver slurry with solid content of 50%, blade coating to obtain coating with thickness of 20 μm, treating at 175 deg.C for 30min, and measuring resistivity of silver film to obtain silver film with resistivity of 1×10 -5 Omega cm. The morphology is shown in figure 3, and the morphology after low-temperature sintering is shown in figure 4.
Example 3: preparation of granular and flaky mixed nano silver
The preparation method of the granular and flaky nano silver mixture comprises the following steps: 10g PVP with average molecular weight of 58000 is dissolved in 100mL glycol under constant stirring at normal temperature; then dispersing 10g of silver oxalate powder in the PVP solution, and stirring and carrying out ultrasonic treatment to obtain a uniform dispersion liquid without precipitation; the above-mentioned materials are mixedTransferring the dispersion liquid into an oil bath heated reaction kettle, heating the mixed liquid to 120 ℃ under the condition of continuous stirring, reacting for 2 hours at constant temperature, stopping heating, and naturally cooling the reaction system to room temperature. Adding 250mL of acetone into the mixture after reaction under continuous stirring, standing for 30min, naturally settling nano silver, pouring out supernatant, dispersing precipitate containing nano silver into 500mL of ethanol, centrifuging for 30min under the condition of 3000rpm, and cleaning to obtain precipitate; and then repeatedly washing for 5 times through ceramic membrane dynamic filtration, finally centrifuging to obtain a solid product, dispersing the solid product in 100mL, and obtaining silver powder for later use through freeze drying. The prepared nano silver mainly comprises two shapes of particles and flakes, wherein the particle size of the particle nano silver is 50-150nm, the flakes of the nano silver mainly comprise triangles, the flake diameter is about 200-800nm, and the thick bottom is about 50-100nm. Dispersing the above nanometer silver in isopropanol to obtain silver slurry with solid content of 50%, blade coating to obtain coating with thickness of 20 μm, treating at 175 deg.C for 30min, and measuring resistivity of silver film to obtain silver film with resistivity of 5×10 -6 Omega cm. The morphology is shown in fig. 5, and the morphology after low-temperature sintering is shown in fig. 6.
Comparative example 1: preparation of granular nano silver
A preparation method of granular nano silver only, which comprises the following steps: at normal temperature, 10g PVP with average molecular weight of 360000 is dissolved in 100mL deionized water by continuous stirring; then dispersing 10g of silver oxalate powder in the PVP solution, and stirring and carrying out ultrasonic treatment to obtain a uniform dispersion liquid without precipitation; transferring the dispersion liquid into an oil bath heated reaction kettle, heating the mixed liquid until boiling and reacting for 4 hours at constant temperature under the condition of continuous stirring, stopping heating, and naturally cooling the reaction system to room temperature. Adding 250mL of acetone into the mixture after reaction under continuous stirring, standing for 30min, naturally settling nano silver, pouring out supernatant, dispersing precipitate containing nano silver into 500mL of ethanol, and centrifuging for 30min under the condition of 3000rpm to clean nano silver to obtain precipitate; repeatedly cleaning for 5 times through ceramic membrane dynamic filtration, finally centrifuging to obtain a solid product, and adding 1:1, mixing the isopropyl alcohol into silver paste by using a planetary mixing device for later use.The prepared nano silver is granular, and the grain diameter is 50-100nm. Dispersing the above nanometer silver in isopropanol to obtain silver slurry with solid content of 50%, blade coating to obtain coating with thickness of 20 μm, treating at 175 deg.C for 30min, and measuring resistivity of silver film to 2×10 -5 Omega cm. The morphology is shown in figure 7.
Comparative example 2: micron-sized silver
A preparation method of micron-sized silver, which comprises the following steps: at normal temperature, 10g PVP with average molecular weight of 10000 is dissolved in 100mL benzyl alcohol by continuous stirring; then dispersing 10g of silver oxalate powder in the PVP solution, and stirring and carrying out ultrasonic treatment to obtain a uniform dispersion liquid without precipitation; transferring the dispersion liquid into an oil bath heated reaction kettle, heating the mixed liquid to 110 ℃ under the condition of continuous stirring, reacting for 2 hours at constant temperature, stopping heating, and naturally cooling the reaction system to room temperature. 250mL of acetone is added into the mixture after the reaction under continuous stirring, then the mixture is kept stand for 30min, nano silver is naturally settled, supernatant liquid is poured out, precipitate containing nano silver is dispersed in 500mL of ethanol, and the mixture is centrifuged for 10min under the condition of 3000rpm, thus obtaining precipitate. The prepared nano silver is granular, the grain diameter is 0.5-4 mu m, the grain diameter is too large, and the nano silver cannot be stably dispersed into silver paste and formed into a film, and the low-temperature sintering characteristic is avoided. The morphology is shown in figure 8.
Comparative example 3:
10g PVP with average molecular weight of 58000 is dissolved in 100mL glycol under constant stirring at normal temperature; then dispersing 10g of silver acetate powder in the PVP solution, and stirring and carrying out ultrasonic treatment to obtain a uniform dispersion liquid without precipitation; transferring the dispersion liquid into an oil bath heated reaction kettle, heating the mixed liquid to 100 ℃ under the condition of continuous stirring, reacting at constant temperature for 12 hours, stopping heating, and naturally cooling the reaction system to room temperature. The reaction liquid turns from white to brown and contains large-particle solids, and after the solids naturally settle, the supernatant is poured off, and deionized water is added for repeated natural settlement and washing. The separated solid powder was dried and XRD tests revealed that the obtained solid was mainly silver oxide and unreacted silver acetate. The morphology is shown in figure 9.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between these technical feature combinations, they should be considered as the scope of the description.
Claims (7)
1. The preparation method of the polymorphic low-temperature sinterable nano silver is characterized by comprising the following steps of:
(1) Weighing insoluble silver salt, adding the insoluble silver salt into a solvent containing 5% -20% of polymer dispersing agent, and alternately carrying out mechanical stirring and ultrasonic dispersing for 10-60min to obtain uniform mixed solution A;
the solvent comprises at least one of water, ethylene glycol, diethylene glycol, polyethylene glycol, glycerol, 1, 2-propylene glycol and n-butanol;
(2) Heating the mixed solution A obtained in the step (1) to 80-140 ℃ under stirring, preserving heat for 1-2 h, and naturally cooling to room temperature to obtain a mixed solution B containing nano silver products;
(3) Adding a poor solvent of the polymer dispersing agent into the mixed solution B obtained in the step (2) under stirring, stirring until flocculation occurs, stopping stirring, and standing to obtain a precipitate;
the volume ratio of the poor solvent of the polymer dispersant to the solvent in the step (1) is 1-3:1;
(4) Dispersing the precipitate in an alcohol solvent by stirring and ultrasonic, centrifuging, collecting a solid product, dispersing in the alcohol solvent, filtering for 3-5 times, centrifuging again to obtain a solid product, dissolving in water, and freeze-drying to obtain the multi-morphology low-temperature sinterable nano silver;
the mass volume ratio of the insoluble silver salt to the solvent in the step (1) is 0.3-2kg/L, the speed of mechanical stirring is 100-500r/min, and the power of ultrasonic dispersion is 50-300W;
the insoluble silver salt is silver oxalate;
the shape of the multi-morphology low-temperature sinterable nano silver comprises at least two mixed nano silver of nano particles, nano sheets and nano rods;
the particle size of the nano particles is 20-150nm, the sheet diameter of the nano sheets is 200-5000nm, the thickness is 20-100nm, the diameter of the nano rods is 30-100nm, and the length is 1-10 mm.
2. The method for preparing the polymorphic low-temperature sinterable nano-silver according to claim 1, wherein the method comprises the following steps of
The polymer dispersant comprises at least one of polyvinylpyrrolidone having an average molecular weight of 10000-360000.
3. The method for preparing polymorphic low-temperature sinterable nano-silver according to claim 1, wherein the centrifugation conditions in step (4) are: the centrifugal speed is 3000-8000r/min, the centrifugal time is 10-30min, and the filtering comprises a ceramic membrane dynamic circulating filtering device.
4. The method for preparing the polymorphic low-temperature sinterable nano-silver according to claim 3, wherein the pore diameter of the ceramic membrane dynamic circulation filter device is 20-100nm, and the pressure difference is 0.01-0.3MPa.
5. The method of claim 1, wherein the alcohol solvent in step (4) comprises at least one of ethanol, isopropanol, ethylene glycol, n-propanol, n-butanol, diethylene glycol, and benzyl alcohol.
6. A polymorphic low temperature sinterable nanosilver obtainable by a process according to any one of claims 1 to 5.
7. The use of multi-morphology low temperature sinterable nano-silver according to claim 6 as a metallic nanomaterial.
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